U.S. patent application number 16/126250 was filed with the patent office on 2019-03-14 for poly(amide-imide) copolymer, composition for preparing poly(amide-imide) copolymer, article including poly(amide-imide) copolymer, and display device including the article.
The applicant listed for this patent is SAMSUNG ELECTRONICS CO., LTD., SAMSUNG SDI CO., LTD.. Invention is credited to Chanjae AHN, Won Suk CHANG, Sungwon CHOI, Boreum JEONG, A Ra JO.
Application Number | 20190077916 16/126250 |
Document ID | / |
Family ID | 65630653 |
Filed Date | 2019-03-14 |
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United States Patent
Application |
20190077916 |
Kind Code |
A1 |
JO; A Ra ; et al. |
March 14, 2019 |
POLY(AMIDE-IMIDE) COPOLYMER, COMPOSITION FOR PREPARING
POLY(AMIDE-IMIDE) COPOLYMER, ARTICLE INCLUDING POLY(AMIDE-IMIDE)
COPOLYMER, AND DISPLAY DEVICE INCLUDING THE ARTICLE
Abstract
A poly(amide-imide) copolymer that is a reaction product of a
substituted or unsubstituted linear aliphatic diamine including two
terminals, a diamine represented by Chemical Formula 1, a
dicarbonyl compound represented by Chemical Formula 2, and a
tetracarboxylic acid dianhydride represented by Chemical Formula 3:
##STR00001## wherein, in Chemical Formulae 1 to 3, A, R.sup.3,
R.sup.10, R.sup.12, R.sup.13, X, n7 and n8 are the same as defined
in the specification.
Inventors: |
JO; A Ra; (Euiwang-si,
KR) ; AHN; Chanjae; (Suwon-si, KR) ; CHOI;
Sungwon; (Hwaseong-si, KR) ; CHANG; Won Suk;
(Hwaseong-si, KR) ; JEONG; Boreum; (Daejeon,
KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SAMSUNG ELECTRONICS CO., LTD.
SAMSUNG SDI CO., LTD. |
Suwon-si
Yongin-si |
|
KR
KR |
|
|
Family ID: |
65630653 |
Appl. No.: |
16/126250 |
Filed: |
September 10, 2018 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B29K 2079/08 20130101;
C08G 73/1042 20130101; C08G 73/14 20130101; B29C 41/003 20130101;
B29L 2007/008 20130101; C08J 5/18 20130101; B29C 41/46 20130101;
C08G 73/1039 20130101; C08J 2379/08 20130101 |
International
Class: |
C08G 73/14 20060101
C08G073/14; C08J 5/18 20060101 C08J005/18; B29C 41/00 20060101
B29C041/00; B29C 41/46 20060101 B29C041/46 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 8, 2017 |
KR |
10-2017-0115218 |
Claims
1. A poly(amide-imide) copolymer that is a reaction product of a
substituted or unsubstituted linear aliphatic diamine comprising
two terminals, a diamine represented by Chemical Formula 1, a
dicarbonyl compound represented by Chemical Formula 2, and a
tetracarboxylic acid dianhydride represented by Chemical Formula 3:
NH.sub.2-A-NH.sub.2 Chemical Formula 1 wherein in Chemical Formula
1, A is a ring system comprising two or more C6 to C30 aromatic
rings linked by a single bond, wherein each of the two or more
aromatic rings is independently unsubstituted or substituted by an
electron-withdrawing group; ##STR00026## wherein, in Chemical
Formula 2, R.sup.3 is a substituted or unsubstituted phenylene or a
substituted or unsubstituted biphenylene group, and each X is an
identical or different halogen atom; ##STR00027## wherein, in
Chemical Formula 3, R.sup.10 is a single bond, --O--, --S--,
--C(.dbd.O)--, --CH(OH)--, --C(.dbd.O)NH--, --S(.dbd.O).sub.2--,
--Si(CH.sub.3).sub.2--, --(CH.sub.2).sub.p--, --(CF.sub.2).sub.q--,
--C(C.sub.nH.sub.2n+1).sub.2--, --C(C.sub.nF.sub.2n+1).sub.2--,
--(CH.sub.2).sub.pC(C.sub.nH.sub.2n+1).sub.2(CH.sub.2).sub.q--, or
--(CH.sub.2).sub.pC(C.sub.nF.sub.2n+1).sub.2(CH.sub.2).sub.q--
wherein 1.ltoreq.n.ltoreq.10, 1.ltoreq.p.ltoreq.10, and
1.ltoreq.q.ltoreq.10, R.sup.12 and R.sup.13 are each independently
a halogen, a hydroxy group, a substituted or unsubstituted C1 to
C10 aliphatic organic group, a substituted or unsubstituted C6 to
C20 aromatic organic group, an alkoxy group of formula
--OR.sup.201, wherein R.sup.201 is a C1 to C10 aliphatic organic
group, or a silyl group of formula --SiR.sup.210R.sup.211R.sup.212,
wherein R.sup.210, R.sup.211, and R.sup.212 are each independently
hydrogen ora C1 to C10 aliphatic organic group, and n7 and n8 are
each independently an integer ranging from 0 to 3.
2. The poly(amide-imide) copolymer according to claim 1, wherein
the substituted or unsubstituted linear aliphatic diamine comprises
an amino group located at each end of the two terminals thereof,
and wherein the substituted or unsubstituted linear aliphatic
diamine is a substituted or unsubstituted C1 to C30 saturated or
unsaturated linear aliphatic diamine.
3. The poly(amide-imide) copolymer according to claim 1, wherein
the substituted or unsubstituted linear aliphatic diamine includes
an amino group located at each end of the two terminals thereof,
and wherein the substituted or unsubstituted linear aliphatic
diamine is a substituted or unsubstituted C1 to C20 saturated
linear aliphatic diamine.
4. The poly(amide-imide) copolymer according to claim 1, wherein
the substituted or unsubstituted linear aliphatic diamine is
selected from methylene diamine, ethylene diamine, 1,3-propane
diamine, 1,4-tetramethylene diamine, 1,5-pentamethylene diamine,
1,6-hexamethylene diamine, 1,7-heptamethylene diamine,
1,8-octamethylene diamine, 1,9-nanomethylene diamine,
1,10-decamehtylene diamine, 1,11-undecamethylene diamine,
1,12-dodecamethylene diamine, and a combination thereof.
5. The poly(amide-imide) copolymer according to claim 1, wherein
the diamine represented by Chemical Formula 1 comprises a ring
system comprising two C6 to C12 aromatic rings linked by a single
bond, wherein each of the two C6 to C12 aromatic rings are
independently substituted by an electron-withdrawing group selected
from a halogen atom, a nitro group, a cyano group, a C1 or C2
haloalkyl group, a C2 to C6 alkanoyl group, and a C2 to C6 ester
group.
6. The poly(amide-imide) copolymer according to claim 1, wherein
the diamine represented by Chemical Formula 1 comprises at least
one selected from the diamines represented by chemical formulae:
##STR00028##
7. The poly(amide-imide) copolymer according to claim 1, wherein
the diamine represented by Chemical Formula 1 comprises a diamine
represented by Chemical Formula A: ##STR00029##
8. The poly(amide-imide) copolymer according to claim 1, wherein in
Chemical Formula 2, R.sup.3 is a phenylene group, and each X is
independently Cl or Br.
9. The poly(amide-imide) copolymer according to claim 1, wherein
the tetracarboxylic acid dianhydride represented by Chemical
Formula 3 comprises at least one selected from 3,3',4,4'-biphenyl
tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfone
tetracarboxylic dianhydride (DSDA),
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and
4,4'-oxydiphthalic anhydride (ODPA).
10. The poly(amide-imide) copolymer according to claim 1, wherein
the tetracarboxylic acid dianhydride represented by Chemical
Formula 3 comprises a combination of 3,3',4,4'-biphenyl
tetracarboxylic dianhydride and
4,4'-(hexafluoroisopropylidene)diphthalic anhydride.
11. The poly(amide-imide) copolymer according to claim 1, wherein
an amount of the substituted or unsubstituted linear aliphatic
diamine is greater than 20 mole percent and less than 90 mol
percent based on the total amount of the substituted or
unsubstituted linear aliphatic diamine and the diamine represented
by Chemical Formula 1.
12. The poly(amide-imide) copolymer according to claim 1, wherein a
mole ratio of the dicarbonyl compound represented by Chemical
Formula 2 and the tetracarboxylic acid dianhydride represented by
Chemical Formula 3 is 10 to 80:90 to 20.
13. A composition for preparing a poly(amide-imide) copolymer
comprising a substituted or unsubstituted linear aliphatic diamine,
a compound represented by Chemical Formula 4, and a tetracarboxylic
acid dianhydride represented by Chemical Formula 3: ##STR00030##
wherein, in Chemical Formula 4, R.sup.3 is a substituted or
unsubstituted phenylene or a substituted or unsubstituted
biphenylene group, n0 is a number greater than or equal to 0, and
Ar.sup.1 and Ar.sup.2 are each independently represented by
Chemical Formula 5: ##STR00031## wherein, in Chemical Formula 5,
R.sup.6 and R.sup.7 are each independently an electron withdrawing
group selected from --CF.sub.3, --CCl.sub.3, --CBr.sub.3,
--Cl.sub.3, --NO.sub.2, --CN, --C(.dbd.O)CH3, and
--CO.sub.2C.sub.2H.sub.5, R.sup.8 and R.sup.9 are each
independently a halogen, a hydroxy group, a substituted or
unsubstituted C1 to C10 aliphatic organic group, a substituted or
unsubstituted C6 to C20 aromatic organic group, an alkoxy group of
formula --OR.sup.204, wherein R.sup.204 is a C1 to C10 aliphatic
organic group, or a silyl group of formula
--SiR.sup.205R.sup.206R.sup.207 wherein R.sup.205, R.sup.206, and
R.sup.207 are each independently hydrogen or a C1 to C10 aliphatic
organic group, n3 is an integer ranging from 1 to 4, n5 is an
integer ranging from 0 to 3, provided that n3+n5 is an integer
ranging from 1 to 4, and n4 is an integer ranging from 1 to 4, n6
is an integer ranging from 0 to 3, provided that n4+n6 is an
integer ranging from 1 to 4; ##STR00032## wherein, in Chemical
Formula 3, R.sup.10 is a single bond, --O--, --S--, --C(.dbd.O)--,
--CH(OH)--, --C(.dbd.O)NH--, --S(.dbd.O).sub.2--,
--Si(CH.sub.3).sub.2--, --(CH.sub.2).sub.p--, --(CF.sub.2).sub.q--,
--C(C.sub.nH.sub.2n+1).sub.2--, --C(C.sub.nF.sub.2n+1).sub.2--,
--(CH.sub.2).sub.pC(C.sub.nH.sub.2n+1).sub.2(CH.sub.2).sub.q--, or
--(CH.sub.2).sub.pC(C.sub.nF.sub.2n+1).sub.2(CH.sub.2).sub.q--
wherein 1.ltoreq.n.ltoreq.10, 1.ltoreq.p.ltoreq.10, and
1.ltoreq.q.ltoreq.10, R.sup.12 and R.sup.13 are each independently
a halogen, a hydroxy group, a substituted or unsubstituted C1 to
C10 aliphatic organic group, a substituted or unsubstituted C6 to
C20 aromatic organic group, an alkoxy group of formula
--OR.sup.201, wherein R.sup.201 is a C1 to C10 aliphatic organic
group, or a silyl group of formula --SiR.sup.210R.sup.211R.sup.212,
wherein R.sup.210, R.sup.211, and R.sup.212 are each independently
hydrogen ora C1 to C10 aliphatic organic group, and n7 and n8 are
each independently an integer ranging from 0 to 3.
14. The composition for preparing a poly(amide-imide) copolymer
according to claim 13, wherein the composition further comprises a
diamine represented by Chemical Formula 1: NH.sub.2-A-NH.sub.2
Chemical Formula 1 wherein in Chemical Formula 1, A is a ring
system comprising two or more C6 to C30 aromatic rings linked by a
single bond, wherein each of the two or more aromatic rings is
independently unsubstituted or substituted by an
electron-withdrawing group.
15. The composition for preparing a poly(amide-imide) copolymer
according to claim 13, wherein the substituted or unsubstituted
linear aliphatic diamine comprises two terminals, wherein the
substituted or unsubstituted linear aliphatic diamine comprises an
amino group located at each end of the two terminals thereof, and
wherein the substituted or unsubstituted linear aliphatic diamine
is a substituted or unsubstituted C1 to C30 saturated or
unsaturated linear aliphatic diamine.
16. The composition for preparing a poly(amide-imide) copolymer
according to claim 13, wherein the substituted or unsubstituted
linear aliphatic diamine comprises two terminals, wherein the
substituted or unsubstituted linear aliphatic diamine comprises an
amino group located at each end of the two terminals thereof, and
wherein the substituted or unsubstituted linear aliphatic diamine
is a substituted or unsubstituted C1 to C20 saturated linear
aliphatic diamine.
17. The composition for preparing a poly(amide-imide) copolymer
according to claim 13, wherein the tetracarboxylic acid dianhydride
represented by Chemical Formula 3 comprises a combination of the
compound represented by Chemical Formula 3-1, and the compound
represented by Chemical Formula 3-2: ##STR00033##
18. An article comprising a poly(amide-imide) copolymer according
to claim 1.
19. The article according to claim 18, wherein the article
comprises a film, and wherein the film has a toughness of greater
than or equal to 1,000 Joules.times.reverse cubic
meters.times.10.sup.4 (Joulm.sup.-310.sup.4), when the film has a
thickness of about 30 micrometers to about 100 micrometers.
20. A display device comprising the article according to claim 18.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application claims priority to Korean Patent
Application No. 10-2017-0115218, filed on Sep. 8, 2017, and all the
benefits accruing therefrom under 35 U.S.C. .sctn. 119, the content
of which is incorporated herein in its entirety by reference.
BACKGROUND
1. Field
[0002] This disclosure relates to a poly(amide-imide) copolymer, a
composition for preparing a poly(amide-imide) copolymer, an article
including a poly(amide-imide) copolymer, and to a display device
including the article. 2. Description of the Related Art
[0003] A flexible display, which is not restricted by time and
place, that is thin and flexible like paper, ultra light, and
consumes a small amount of electricity, has been increasingly in
demand as a display for visualizing various information and
delivering it to the users. The flexible display may be realized by
using a flexible substrate, organic and inorganic materials for a
low temperature process, flexible electronics, encapsulation,
packaging, and the like.
[0004] A transparent plastic film for replacing a conventional
window cover glass to be used in a flexible display must have high
toughness and excellent optical properties. Desired optical
properties include high light transmittance, low haze, low
yellowness index, low Yl difference after exposure to UV light, and
the like.
[0005] There still remains a need for polymers having excellent
optical and mechanical properties that could be used in transparent
plastic films.
SUMMARY
[0006] An embodiment provides a poly(amide-imide) copolymer having
improved optical and mechanical properties.
[0007] Another embodiment provides a composition for preparing a
poly(amide-imide) copolymer.
[0008] Still another embodiment provides an article including a
poly(amide-imide) copolymer.
[0009] Yet another embodiment provides a display device including
an article including the poly(amide-imide) copolymer.
[0010] According to an embodiment, provided is a poly(amide-imide)
copolymer that is a reaction product of a substituted or
unsubstituted linear aliphatic diamine including two terminals, a
diamine represented by Chemical Formula 1, a dicarbonyl compound
represented by Chemical Formula 2, and a tetracarboxylic acid
dianhydride represented by Chemical Formula 3:
NH.sub.2-A-NH.sub.2 Chemical Formula 1
[0011] wherein in Chemical Formula 1,
[0012] A is a ring system including two or more C6 to C30 aromatic
rings linked by a single bond, wherein each of the two or more of
the aromatic rings is independently unsubstituted or substituted by
an electron-withdrawing group;
##STR00002##
[0013] wherein, in Chemical Formula 2,
[0014] R.sup.3 is a substituted or unsubstituted phenylene or a
substituted or unsubstituted biphenylene group, and each X is an
identical or a different halogen atom,
##STR00003##
[0015] wherein, in Chemical Formula 3,
[0016] R.sup.10 is a single bond, --O--, --S--, --C(.dbd.O)--,
--CH(OH)--, --C(.dbd.O)NH--, --S(.dbd.O).sub.2--,
--Si(CH.sub.3).sub.2--, --(CH.sub.2).sub.p--, --(CF.sub.2).sub.q--,
--C(C.sub.nH.sub.2n+1).sub.2--, --C(C.sub.nF.sub.2n+1).sub.2--,
--(CH.sub.2).sub.pC(C.sub.nH.sub.2n+1).sub.2(CH.sub.2).sub.q--, or
--(CH.sub.2).sub.pC(C.sub.nF.sub.2n+1).sub.2(CH.sub.2).sub.q--
wherein 1.ltoreq.n.ltoreq.10, 1.ltoreq.p.ltoreq.10, and
1.ltoreq.q.ltoreq.10,
[0017] R.sup.12 and R.sup.13 are each independently a halogen, a
hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic
organic group, a substituted or unsubstituted C6 to C20 aromatic
organic group, an alkoxy group of formula --OR.sup.201, wherein
R.sup.201 is a C1 to C10 aliphatic organic group, or a silyl group
of formula --SiR.sup.210R.sup.211R.sup.212, wherein R.sup.210,
R.sup.211, and R.sup.212 are each independently hydrogen or a C1 to
C10 aliphatic organic group,
[0018] n7 and n8 are each independently an integer ranging from 0
to 3.
[0019] The substituted or unsubstituted linear aliphatic diamine
includes an amino group located at each end of the two terminals
thereof, and may be a substituted or unsubstituted C1 to C30
saturated or unsaturated linear aliphatic diamine.
[0020] The substituted or unsubstituted linear aliphatic diamine
includes an amino group located at each end of the two terminals
thereof, and may be a substituted or unsubstituted C1 to C20
saturated linear aliphatic diamine.
[0021] The substituted or unsubstituted linear aliphatic diamine
may be selected from methylene diamine, ethylene diamine,
1,3-propane diamine, 1,4-tetramethylene diamine, 1,5-pentamethylene
diamine, 1,6-hexamethylene diamine, 1,7-heptamethylene diamine,
1,8-octamethylene diamine, 1,9-nanomethylene diamine,
1,10-decamehtylene diamine, 1,11-undecamethylene diamine,
1,12-dodecamethylene diamine, and a combination thereof.
[0022] The diamine represented by Chemical Formula 1 may have a
ring system including two C6 to C12 aromatic rings linked by a
single bond, wherein each of the two C6 to C12 aromatic rings may
be substituted by an electron-withdrawing group selected from a
halogen atom, a nitro group, a cyano group, a C1 or C2 haloalkyl
group, a C2 to C6 alkanoyl group, and a C1 to C6 ester group.
[0023] The diamine represented by Chemical Formula 1 may include at
least one selected from the diamines represented by chemical
formulae:
##STR00004##
[0024] The diamine represented by Chemical Formula 1 may include
the diamine represented by Chemical Formula A:
##STR00005##
[0025] In Chemical Formula 2, R.sup.3 may be a phenylene group, and
each X may be independently Cl or Br.
[0026] The tetracarboxylic acid dianhydride represented by Chemical
Formula 3 may include at least one selected from 3,3',4,4'-biphenyl
tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfone
tetracarboxylic dianhydride (DSDA),
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and
4,4'-oxydiphthalic anhydride (ODPA).
[0027] The tetracarboxylic acid dianhydride represented by Chemical
Formula 3 may include a combination of 3,3',4,4'-biphenyl
tetracarboxylic dianhydride (BPDA) and
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA).
[0028] An amount of the substituted or unsubstituted linear
aliphatic diamine may be greater than 20 mole percent and less than
90 mole percent based on the total amount of the substituted or
unsubstituted linear aliphatic diamine and the diamine represented
by Chemical Formula 1.
[0029] A mole ratio of the dicarbonyl compound represented by
Chemical Formula 2 and the tetracarboxylic acid dianhydride
represented by Chemical Formula 3 may be 10 to 80:90 to 20.
[0030] According to an embodiment, provided is a composition for
preparing a poly(amide-imide) copolymer including a substituted or
unsubstituted linear aliphatic diamine, a compound represented by
Chemical Formula 4, and a tetracarboxylic acid dianhydride
represented by Chemical Formula 3:
##STR00006##
[0031] wherein, in Chemical Formula 4,
[0032] R.sup.3 is a substituted or unsubstituted phenylene or a
substituted or unsubstituted biphenylene group,
[0033] n0 is a number greater than or equal to 0,
[0034] Ar.sup.1 and Ar.sup.2 are each independently represented by
Chemical Formula 5:
##STR00007##
[0035] wherein, in Chemical Formula 5,
[0036] R.sup.6 and R.sup.7 are each independently an electron
withdrawing group selected from --CF.sub.3, --CCl.sub.3,
--CBr.sub.3, --Cl.sub.3, --NO.sub.2, --CN, --C(.dbd.O)CH.sub.3, and
--CO.sub.2C.sub.2H.sub.5,
[0037] R.sup.8 and R.sup.9 are each independently a halogen, a
hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic
organic group, a substituted or unsubstituted C6 to C20 aromatic
organic group, an alkoxy group of formula --OR.sup.204, wherein
R.sup.204 is a C1 to C10 aliphatic organic group, or a silyl group
of formula --SiR.sup.205R.sup.206R.sup.207 wherein R.sup.205,
R.sup.206, and R.sup.207 are each independently hydrogen or a C1 to
C10 aliphatic organic group,
[0038] n3 is an integer ranging from 1 to 4, n5 is an integer
ranging from 0 to 3, provided that n3+n5 is an integer ranging from
1 to 4, and
[0039] n4 is an integer ranging from 1 to 4, n6 is an integer
ranging from 0 to 3, provided that n4+n6 is an integer ranging from
1 to 4;
##STR00008##
[0040] wherein, in Chemical Formula 3,
[0041] R.sup.10 is a single bond, --O--, --S--, --C(.dbd.O)--,
--CH(OH)--, --C(.dbd.O)NH--, --S(.dbd.O).sub.2--,
--Si(CH.sub.3).sub.2--, --(CH.sub.2).sub.p--, --(CF.sub.2).sub.q--,
--C(C.sub.nH.sub.2n+1).sub.2--, --C(C.sub.nF.sub.2n+1).sub.2--,
--(CH.sub.2).sub.pC(C.sub.nH.sub.2n+1).sub.2(CH.sub.2).sub.q--, or
--(CH.sub.2).sub.pC(C.sub.nF.sub.2n+1).sub.2(CH.sub.2).sub.q--
wherein 1.ltoreq.n.ltoreq.10, 1.ltoreq.p.ltoreq.10, and
1.ltoreq.q.ltoreq.10,
[0042] R.sup.12 and R.sup.13 are each independently a halogen, a
hydroxy group, a substituted or unsubstituted Cl to Cl 0 aliphatic
organic group, a substituted or unsubstituted C6 to C20 aromatic
organic group, an alkoxy group of formula --OR.sup.201, wherein
R.sup.201 is a C1 to C10 aliphatic organic group, or a silyl group
of formula --SiR.sup.210R.sup.211R.sup.212, wherein R.sup.210,
R.sup.211, and R.sup.212 are each independently hydrogen ora C1 to
C10 aliphatic organic group, and
[0043] n7 and n8 are each independently an integer ranging from 0
to 3.
[0044] The composition may further include a diamine represented by
Chemical Formula 1:
NH.sub.2-A-NH.sub.2 Chemical Formula 1
[0045] wherein in Chemical Formula 1,
[0046] A is a ring system including two or more C6 to C30 aromatic
rings linked by a single bond, wherein each of the two or more
aromatic rings is independently unsubstituted or substituted by an
electron-withdrawing group.
[0047] The substituted or unsubstituted linear aliphatic diamine
comprises two terminals, wherein the substituted or unsubstituted
linear aliphatic diamine includes an amino group located at each
end of the two terminals thereof, and wherein the substituted or
unsubstituted linear aliphatic diamine may be a substituted or
unsubstituted C1 to C30 saturated or unsaturated linear aliphatic
diamine.
[0048] The substituted or unsubstituted linear aliphatic diamine
includes an amino group located at each end of the two terminals
thereof, and may be a substituted or unsubstituted C1 to C20
saturated linear aliphatic diamine.
[0049] The tetracarboxylic acid dianhydride represented by Chemical
Formula 3 may be a combination of the compound represented by
Chemical Formula 3-1 and the compound represented by Chemical
Formula 3-2:
##STR00009##
[0050] According to another embodiment, provided is an article
including a poly(amide-imide) copolymer according to an
embodiment.
[0051] The article may be a film, wherein the film may have a
toughness of greater than or equal to 1,000 Joules.times.reverse
cubic meters.times.10.sup.4 (Joulm.sup.-310.sup.4), and a
refractive index of less than or equal to 1.68, when the film has a
thickness of about 30 micrometers to about 100 micrometers.
[0052] According to another embodiment, provided is a display
device including an article according to an embodiment.
[0053] Hereinafter, further embodiments will be described in
detail.
DETAILED DESCRIPTION
[0054] This disclosure will be described more fully hereinafter.
This disclosure may, however, be embodied in many different forms
and is not to be construed as limited to the exemplary embodiments
set forth herein.
[0055] It will be understood that when an element is referred to as
being "on" another element, it may be directly on the other element
or intervening elements may be present therebetween. In contrast,
when an element is referred to as being "directly on" another
element, there are no intervening elements present.
[0056] It will be understood that, although the terms first,
second, third etc. may be used herein to describe various elements,
components, regions, layers and/or sections, these elements,
components, regions, layers and/or sections should not be limited
by these terms. These terms are only used to distinguish one
element, component, region, layer or section from another element,
component, region, layer, or section. Thus, a first element,
component, region, layer, or section discussed below could be
termed a second element, component, region, layer, or section
without departing from the teachings of the present
embodiments.
[0057] The terminology used herein is for the purpose of describing
particular embodiments only and is not intended to be limiting. As
used herein, the singular forms "a," "an" and "the" are intended to
include the plural forms as well, unless the context clearly
indicates otherwise. The term "or" means "and/or." As used herein,
the term "and/or" includes any and all combinations of one or more
of the associated listed items. Expressions such as "at least one
of," when preceding a list of elements, modify the entire list of
elements and do not modify the individual elements of the list.
[0058] It will be further understood that the terms "comprises"
and/or "comprising," or "includes" and/or "including" when used in
this specification, specify the presence of stated features,
regions, integers, steps, operations, elements, and/or components,
but do not preclude the presence or addition of one or more other
features, regions, integers, steps, operations, elements,
components, and/or groups thereof.
[0059] Unless otherwise defined, all terms (including technical and
scientific terms) as used herein have the same meaning as commonly
understood by one of ordinary skill in the art to which this
general inventive concept belongs. It will be further understood
that terms, such as those defined in commonly used dictionaries,
should be interpreted as having a meaning that is consistent with
their meaning in the context of the relevant art and the present
disclosure, and will not be interpreted in an idealized or overly
formal sense unless expressly so defined herein.
[0060] "About" or "approximately" as used herein is inclusive of
the stated value and means within an acceptable range of deviation
for the particular value as determined by one of ordinary skill in
the art, considering the measurement in question and the error
associated with measurement of the particular quantity (i.e., the
limitations of the measurement system).
[0061] "Mixture" as used herein is inclusive of all types of
combinations, including blends, alloys, solutions, and the
like.
[0062] As used herein, when a specific definition is not otherwise
provided, the term "substituted" refers to a group or compound
substituted with at least one substituent including a halogen (--F,
--Br, --Cl, or --I), a hydroxy group, a nitro group, a cyano group,
an amino group (--NH.sub.2, --NH(R.sup.100) or
--N(R.sup.101)(R.sup.102), wherein R.sup.100, R.sup.101, and
R.sup.102 are the same or different, and are each independently a
C1 to C10 alkyl group), an amidino group, a hydrazine group, a
hydrazone group, a carboxyl group, an ester group, a ketone group,
a substituted or unsubstituted alkyl group, a substituted or
unsubstituted alicyclic organic group, a substituted or
unsubstituted aryl group, a substituted or unsubstituted alkenyl
group, a substituted or unsubstituted alkynyl group, a substituted
or unsubstituted heteroaryl group, and a substituted or
unsubstituted heterocyclic group, in place of at least one hydrogen
of a functional group, or the substituents may be linked to each
other to provide a ring.
[0063] As used herein, the term "alkyl group" refers to a straight
or branched chain saturated aliphatic hydrocarbon group having the
specified number of carbon atoms and having a valence of one.
Non-limiting examples of the alkyl group are methyl, ethyl, and
propyl.
[0064] As used herein, the term "alkoxy group" refers to
"alkyl-O--", wherein the term "alkyl" has the same meaning as
described above. Non-limiting examples of the alkoxy group are
methoxy, ethoxy, and propoxy.
[0065] As used herein, when a definition is not otherwise provided,
the term "alkanoyl" represents "alkyl-C(.dbd.O)--", wherein the
term "alkyl" has the same meaning as described above.
[0066] As used herein, the term "aryl group", which is used alone
or in combination, refers to an aromatic hydrocarbon group
containing at least one ring. Non-limiting examples of the aryl
group are phenyl, naphthyl, and tetrahydronaphthyl.
[0067] As used herein, the term "alkylene" indicates a straight or
branched saturated aliphatic hydrocarbon group having a valence of
at least two, optionally substituted with one or more substituents
where indicated, provided that the valence of the alkylene group is
not exceeded.
[0068] As used herein, the term "cycloalkylene" indicates a
saturated cyclic hydrocarbon group having a valence of at least
two, optionally substituted with one or more substituents where
indicated, provided that the valence of the cycloalkylene group is
not exceeded.
[0069] As used herein, when a definition is not otherwise provided,
the term "arylene" indicates a divalent or higher valent group
formed by the removal of two or more hydrogen atoms from one or
more rings of an arene, wherein the hydrogen atoms may be removed
from the same or different rings of the arene.
[0070] As used herein, when a specific definition is not otherwise
provided, the term "alkyl group" refers to a C1 to C30 alkyl group,
for example, a C1 to C15 alkyl group, the term "cycloalkyl group"
refers to a C3 to C30 cycloalkyl group, for example, a C3 to C18
cycloalkyl group, the term "alkoxy group" refer to a C1 to C30
alkoxy group, for example, a C1 to C18 alkoxy group, the term
"ester group" refers to a C2 to C30 ester group, for example, a C2
to C18 ester group, the term "ketone group" refers to a C3 to C30
ketone group, for example, a C3 to C18 ketone group, the term "aryl
group" refers to a C6 to C30 aryl group, for example, a C6 to C18
aryl group, the term "alkenyl group" refers to a C2 to C30 alkenyl
group, for example, a C2 to C18 alkenyl group, the term "alkynyl
group" refers to a C2 to C30 alkynyl group, for example, a C2 to
C18 alkynyl group, the term "alkylene group" refers to a C1 to C30
alkylene group, for example, a C1 to C18 alkylene group, and the
term "arylene group" refers to a C6 to C30 arylene group, for
example, a C6 to C16 arylene group.
[0071] As used herein, when a specific definition is not otherwise
provided, the term "aliphatic organic group" refers to a C1 to C30
alkyl group, a C2 to C30 alkenyl group, a C2 to C30 alkynyl group,
a C1 to C30 alkylene group, a C2 to C30 alkenylene group, or a C2
to C30 alkynylene group, for example, a C1 to C15 alkyl group, a C2
to C15 alkenyl group, a C2 to C15 alkynyl group, a C1 to C15
alkylene group, a C2 to C15 alkenylene group, or a C2 to C15
alkynylene group, the term "alicyclic organic group" refers to a C3
to C30 cycloalkyl group, a C3 to C30 cycloalkenyl group, a C3 to
C30 cycloalkynyl group, a C3 to C30 cycloalkylene group, a C3 to
C30 cycloalkenylene group, or a C3 to C30 cycloalkynylene group,
for example, a C3 to C15 cycloalkyl group, a C3 to C15 cycloalkenyl
group, a C3 to C15 cycloalkynyl group, a C3 to C15 cycloalkylene
group, a C3 to C15 cycloalkenylene group, or a C3 to C15
cycloalkynylene group.
[0072] As used herein when a definition is not otherwise provided,
the term "aromatic organic group" refers to a C6 to C30 group
including one aromatic ring, two or more aromatic rings fused
together to provide a condensed ring system, or two or more
moieties independently selected from the foregoing (a single
aromatic ring or a condensed ring system) linked through a single
bond or through a functional group selected from a fluorenylene
group, --O--, --S--, --C(.dbd.O)--, --CH(OH)--,
--S(.dbd.O).sub.2--, --Si(CH.sub.3).sub.2--, --(CH.sub.2).sub.p--,
wherein 1.ltoreq.p.ltoreq.10, --(CF.sub.2).sub.q--, wherein
1.ltoreq.q.ltoreq.10, --C(CH.sub.3).sub.2--, --C(CF.sub.3).sub.2--,
and --C(.dbd.O)NH--, for example, through --S(.dbd.O).sub.2--, for
example a C6 to C30 aryl group or a C6 to C30 arylene group, for
example, a C6 to C16 aryl group ora C6 to C16 arylene group such as
phenylene. An example of an aromatic organic group is a
fluorenylene group.
[0073] As used herein, when a specific definition is not otherwise
provided, the term "heterocyclic group" refers to a C2 to C30
heterocycloalkyl group, a C2 to C30 heterocycloalkylene group, a C2
to C30 heterocycloalkenyl group, a C2 to C30 heterocycloalkenylene
group, a C2 to C30 heterocycloalkynyl group, a C2 to C30
heterocycloalkynylene group, a C2 to C30 heteroaryl group, or a C2
to C30 heteroarylene group including 1 to 3 heteroatoms selected
from O, S, N, P, Si, and a combination thereof in one ring, for
example, a C2 to C15 heterocycloalkyl group, a C2 to C15
heterocycloalkylene group, a C2 to C15 heterocycloalkenyl group, a
C2 to C15 heterocycloalkenylene group, a C2 to C15
heterocycloalkynyl group, a C2 to C15 heterocycloalkynylene group,
a C2 to C15 heteroaryl group, or a C2 to C15 heteroarylene group
including 1 to 3 heteroatoms selected from O, S, N, P, Si, and a
combination thereof, in one ring.
[0074] When a group containing a specified number of carbon atoms
is substituted with any of the groups listed in the preceding
paragraph, the number of carbon atoms in the resulting
"substituted" group is defined as the sum of the carbon atoms
contained in the original (unsubstituted) group and the carbon
atoms (if any) contained in the substituent. For example, when the
term "substituted C1 to C30 alkyl" refers to a C1 to C30 alkyl
group substituted with C6 to C30 aryl group, the total number of
carbon atoms in the resulting aryl substituted alkyl group is C7 to
C60.
[0075] As used herein, when a definition is not otherwise provided,
"combination" commonly refers to mixing or copolymerization.
[0076] As used herein, when a definition is not otherwise provided,
"polyimide" may refer to not only "polyimide" itself which is an
imidization product of a polyamic acid, but also "polyamic acid" or
a combination of the "polyimide" itself and "polyamic acid".
Further, the terms "polyimide" and "polyamic acid" may be
understood as the same material.
[0077] In addition, in the specification, the mark "*" may refer to
a point of attachment to another atom.
[0078] Research efforts towards converting mobile devices, such as,
a mobile phone or a tablet personal computer, and the like, to
light, flexible, and bendable devices are currently ongoing. In
this regard, a flexible and transparent window film for a display
device having high hardness for replacing a rigid glass placed on
top of the mobile devices is desired.
[0079] To be used as a window film, good optical and mechanical
properties are desired. Desired optical properties include high
light transmittance, low yellowness index (YI), low YI difference
after exposure to UV light, low haze, low refractive index (low
reflection index), and the like. Mechanical properties, such as
hardness, may be supplemented with a hard coating layer, but a base
film having high toughness may ensure that a final film has high
mechanical properties.
[0080] A polyimide or poly(amide-imide) copolymer has excellent
mechanical, thermal, and optical properties, and thus, is widely
used as a plastic substrate for a display device, such as an
organic light emitting diode (OLED), liquid crystal display (LCD),
and the like. In order to use polyimide or poly(amide-imide) film
as a window film for a flexible display device, however, further
improved mechanical and optical properties, such as, high hardness
(or modulus), toughness, high light transmittance, low yellowness
index, low refractive index, and the like, are desired. It is
difficult, however, to improve both mechanical and optical
properties of the film at the same time, as the two properties,
especially, tensile modulus and yellowness index of a polyimide or
poly(amide-imide) film are in a trade-off relationship with regard
to each other.
[0081] Meanwhile, in an effort to improve mechanical properties of
a poly(amide-imide) copolymer film, researchers prepared a
poly(amide-imide) copolymer by increasing the amount of an amide
structural unit, or by including a dianhydride having a more rigid
structure. However, the tensile modulus of such poly(amide-imide)
copolymer is barely improved, while optical properties, such as YI,
are deteriorated. In addition, refractive index of a film prepared
from the poly(amide-imide) copolymer may increase to boost
reflection index, or the toughness of the film may reduce.
[0082] The inventors of the subject matter of the present
application have studied to develop a poly(amide-imide) copolymer
having good optical properties, as well as improved toughness, and
a composition for preparing the poly(amide-imide). As a result,
they have found a poly(amide-imide) copolymer prepared by
copolymerizing an aromatic tetracarboxylic dianhydride, an aromatic
diamine, and an aromatic dicarbonyl compound, as monomers
conventionally used for preparing a poly(amide-imide), and an
additional substituted or unsubstituted linear aliphatic diamine,
exhibits greatly improved toughness, as well as excellent optical
properties. Moreover, the prepared poly(amide-imide) has a reduced
glass transition temperature (T.sub.g) as the polymer backbone has
increased flexibility and segmental motion derived from the linear
aliphatic diamine, and thus, may be made to a film at a lower
temperature. This may lead to the cost reduction of fabricating a
film. Further, as T.sub.g becomes lower, the amount of solvent
remained in a final article, such as, for example, a film,
reduces.
[0083] Accordingly, an embodiment provides a poly(amide-imide)
copolymer that is a reaction product of a substituted or
unsubstituted linear aliphatic diamine, a diamine represented by
Chemical Formula 1, a dicarbonyl compound represented by Chemical
Formula 2, and a tetracarboxylic acid dianhydride represented by
Chemical Formula 3:
NH.sub.2-A-NH.sub.2 Chemical Formula 1
[0084] wherein in Chemical Formula 1,
[0085] A is a ring system including two or more C6 to C30 aromatic
rings linked by a single bond, wherein each of the two or more
aromatic rings is independently unsubstituted or substituted by an
electron-withdrawing group;
##STR00010##
[0086] wherein, in Chemical Formula 2,
[0087] R.sup.3 is a substituted or unsubstituted phenylene or a
substituted or unsubstituted biphenylene group, and each X is an
identical or a different halogen atom.
##STR00011##
[0088] wherein, in Chemical Formula 3,
[0089] R.sup.10 is a single bond, --O--, --S--, --C(.dbd.O)--,
--CH(OH)--, --C(.dbd.O)NH--, --S(.dbd.O).sub.2--,
--Si(CH.sub.3).sub.2--, --(CH.sub.2).sub.p--, --(CF.sub.2).sub.q--,
--C(C.sub.nH.sub.2n+1).sub.2--, --C(C.sub.nF.sub.2n+1).sub.2--,
--(CH.sub.2).sub.pC(C.sub.nH.sub.2n+1).sub.2(CH.sub.2).sub.q--, or
--(CH.sub.2).sub.pC(C.sub.nF.sub.2n+1).sub.2(CH.sub.2).sub.q--
wherein 1.ltoreq.n.ltoreq.10, 1.ltoreq.p.ltoreq.10, and
1.ltoreq.q.ltoreq.10,
[0090] R.sup.12 and R.sup.13 are each independently a halogen, a
hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic
organic group, a substituted or unsubstituted C6 to C20 aromatic
organic group, an alkoxy group of formula --OR.sup.201, wherein
R.sup.201 is a C1 to C10 aliphatic organic group, or a silyl group
of formula --SiR.sup.210R.sup.211R.sup.212, wherein R.sup.210,
R.sup.211, and R.sup.212 are each independently hydrogen or a C1 to
C10 aliphatic organic group,
[0091] n7 and n8 are each independently an integer ranging from 0
to 3.
[0092] The substituted or unsubstituted linear aliphatic diamine
includes an amino group located at each end of the two terminals
thereof, and may be a substituted or unsubstituted C1 to C30
saturated or unsaturated linear aliphatic diamine. For example, the
substituted or unsubstituted linear aliphatic diamine includes an
amino group located at each end of the two terminals thereof, and
the linear aliphatic diamine may be a substituted or unsubstituted
C1 to C30 saturated linear aliphatic diamine, or a substituted or
unsubstituted C2 to C30 unsaturated linear aliphatic diamine having
one or more carbon-carbon double bond or carbon-carbon triple
bond.
[0093] When the substituted or unsubstituted linear aliphatic
diamine is a substituted linear aliphatic diamine, the substitution
indicates that one or more hydrogen bound to a carbon atom is
substituted by another atom or a group selected from, for example,
deuterium, a halogen, hydroxyl group, a cyano group, a nitro group,
a haloalkyl group, a carboxyl group, an epoxy group, a
glicydoxypropyl group, and the like, but is not limited thereto,
and may be substituted by any atom or group that does not adversely
affect the optical or mechanical properties of the
poly(amide-imide) copolymer prepared therefrom.
[0094] In an exemplary embodiment, the substituted or unsubstituted
linear aliphatic diamine includes an amino group located at each
end of the two terminals thereof, and may be an unsubstituted C1 to
C30 saturated linear aliphatic diamine, for example, an
unsubstituted C1 to C20 saturated linear aliphatic diamine, for
example, an unsubstituted C1 to C16 saturated linear aliphatic
diamine, for example, and an unsubstituted C1 to C12 saturated
linear aliphatic diamine, and for example, may be selected from
methylene diamine, ethylene diamine, 1,3-propane diamine,
1,4-tetramethylene diamine, 1,5-pentamethylene diamine,
1,6-hexamethylene diamine, 1,7-heptamethylene diamine,
1,8-octamethylene diamine, 1,9-nanomethylene diamine,
1,10-decamehtylene diamine, 1,11-undecamethylene diamine,
1,12-dodecamethylene diamine, or a combination thereof, but is not
limited thereto.
[0095] Meanwhile, although the linear aliphatic diamines
exemplified above are those having a straight chain, the linear
aliphatic diamine is not limited thereto, but may also include
those linear but having a branch from a carbon atom in the straight
chain.
[0096] The diamine represented by Chemical Formula 1 may have a
ring system including two C6 to C12 aromatic rings linked by a
single bond, wherein each of the two C6 to C12 aromatic rings may
independently be substituted by an electron-withdrawing group
selected from an halogen atom, a nitro group, a cyano group, a C1
or C2 haloalkyl group, a C2 to C6 alkanoyl group, or a C1 to C6
ester group.
[0097] In an exemplary embodiment, the electron-withdrawing group
substituted to each of the aromatic rings of the diamine
represented by Chemical Formula 1 may be selected from an halogen
atom, --CF.sub.3, --CCl.sub.3, --CBr.sub.3, or --Cl.sub.3.
[0098] The diamine represented by Chemical Formula 1 may include at
least one selected from the diamines represented by the following
chemical formulae:
##STR00012##
[0099] The diamine represented by Chemical Formula 1 may include a
diamine represented by Chemical Formula A, i.e.,
2,2'-bis(trifluoromethyl)benzidine (TFDB):
##STR00013##
[0100] In Chemical Formula 2, R.sup.3 may be a phenylene group, and
each X may be independently Cl or Br.
[0101] In an exemplary embodiment, the dicarbonyl compound
represented by Chemical Formula 3 may be terephthaloyl dichloride
(TPCI).
[0102] The tetracarboxylic acid dianhydride represented by Chemical
Formula 3 may include at least one selected from 3,3',4,4'-biphenyl
tetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenylsulfone
tetracarboxylic dianhydride (DSDA),
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and
4,4'-oxydiphthalic anhydride (ODPA), and is not limited
thereto.
[0103] In an exemplary embodiment, the tetracarboxylic acid
dianhydride represented by Chemical Formula 3 may be a combination
of the compound represented by Chemical Formula 3 wherein R.sup.10
is a single bond, and both n7 and n8 are 0, that is, for example,
3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA), and the
compound represented by Chemical Formula 3 wherein R.sup.10 is
--C(C.sub.nF.sub.2n+1).sub.2-- wherein 1.ltoreq.n.ltoreq.10, and
both n7 and n8 are 0, that is, for example,
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA).
[0104] At least one of the substituted or unsubstituted linear
aliphatic diamine and the diamine represented by Chemical Formula 1
may react with a dicarbonyl compound represented by Chemical
Formula 2 to provide an amide structural unit in a
poly(amide-imide) copolymer, and at least one of the substituted or
unsubstituted linear aliphatic diamine and the diamine represented
by Chemical Formula 1 may react with a tetracarboxylic acid
dianhydride represented by Chemical Formula 3 to provide an imide
structural unit in a poly(amide-imide) copolymer.
[0105] A conventional method for preparing a poly(amide-imide)
copolymer may include preparing an amide structural unit by
reacting a dicarbonyl compound represented by Chemical Formula 2,
such as, for example, a dicarbonyl chloride, with a diamine, such
as, for example, at least one of the substituted or unsubstituted
linear aliphatic diamine and the diamine represented by Chemical
Formula 1, to prepare an amide structural unit, and further adding
and reacting an additional diamine, such as, for example, at least
one of the substituted or unsubstituted linear aliphatic diamine
and the diamine represented by Chemical Formula 1, with a
tetracarboxylic acid dianhydride, for example, a tetracarboxylic
acid dianhydride represented by Chemical Formula 3, to prepare an
amic acid structural unit, as well as to link the prepared amide
structural unit and the amic acid structural unit to provide a
poly(amide-amic acid) copolymer. Thus prepared poly(amide-amic
acid) copolymer may be partially or completely imidized by chemical
and/or thermal imidization reaction. Then, the obtained
poly(amide-amic acid and/or imide) copolymer may be precipitated,
filtered, and/or further heat-treated to provide a final
poly(amide-imide) copolymer. This method is well known to persons
skilled in the art to which the present inventive concept
pertains.
[0106] An amide structural unit prepared by reacting a substituted
or unsubstituted linear aliphatic diamine, for example, an
unsubstituted linear aliphatic saturated diamine, and a dicarbonyl
compound represented by Chemical Formula 2 may be represented by
Chemical Formula 7, and an amide structural unit prepared by
reacting a diamine represented by Chemical Formula 1 and a
dicarbonyl compound represented by Chemical Formula 2 may be
represented by Chemical Formula 8:
##STR00014##
[0107] wherein in Chemical Formula 7,
[0108] R.sup.3 is the same as defined for Chemical Formula 3,
and
[0109] n is an integer of greater than or equal to 1, for example,
an integer ranging from 1 to 30.
##STR00015##
[0110] wherein in Chemical Formula 8,
[0111] R.sup.3 is the same as defined for Chemical Formula 3, and A
is the same as defined for Chemical Formula 1.
[0112] Meanwhile, an imide structural unit prepared by reacting a
substituted or unsubstituted linear aliphatic diamine, for example,
an unsubstituted linear aliphatic saturated diamine, and a
tetracarboxylic acid dianhydride represented by Chemical Formula 3
may be represented by Chemical Formula 9, and an imide structural
unit prepared by reacting a diamine represented by Chemical Formula
1 and a tetracarboxylic acid dianhydride represented by Chemical
Formula 3 may be represented by Chemical Formula 10:
##STR00016##
[0113] wherein in Chemical Formula 9,
[0114] each of R.sup.10, R.sup.12, R.sup.13, n7 and n8 are the same
as defined for Chemical Formula 3, and
[0115] n is an integer of greater than or equal to 1, for example,
an integer ranging from 1 to 30;
##STR00017##
[0116] wherein in Chemical Formula 10,
[0117] A is the same as defined for Chemical Formula 1, and
[0118] R.sup.10, R.sup.12, R.sup.13, n7 and n8 are the same as
defined for Chemical Formula 3.
[0119] Therefore, a poly(amide-imide) copolymer according to an
embodiment may include an amide structural unit represented by at
least one of Chemical Formula 7 and Chemical Formula 8, and an
imide structural unit represented by at least one of Chemical
Formula 9 and Chemical Formula 10, provided that the
poly(amide-imide) copolymer is not consisting of an amide
structural unit represented by Chemical Formula 7 and an imide
structural unit represented by Chemical Formula 9, or of an amide
structural unit represented by Chemical Formula 8 and an imide
structural unit represented by Chemical Formula 10.
[0120] The substituted or unsubstituted linear aliphatic diamine
may be included in an amount of less than 90 mole percent (mole %),
for example, greater than 20 mole % and less than 90 mole %, for
example, greater than or equal to about 25 mole % and less than or
equal to about 85 mole %, and for example, greater than or equal to
about 30 mole % and less than or equal to about 80 mole %, based on
the total amount of the substituted or unsubstituted linear
aliphatic diamine and the diamine represented by Chemical Formula
1.
[0121] By including the substituted or unsubstituted linear
aliphatic diamine, along with the diamine represented by Chemical
Formula 1, in the above range, and reacting them with a dicarbonyl
compound represented by Chemical Formula 2 and a tetracarboxylic
acid dianhydride represented by Chemical Formula 3, thus prepared
poly(amide-imide) copolymer may have good mechanical properties,
such as, for example, a toughness of greater than or equal to about
1,000 Joulm.sup.-310.sup.4, a low T.sub.g, such as, for example,
less than 270.degree. C., as well as excellent optical
properties.
[0122] If the amount of the substituted or unsubstituted linear
aliphatic diamine is less than or equal to 20 mole % based on the
total amount of the diamines, improvement in toughness may be
hardly expected, while if the amount is greater than or equal to 90
mole % based on the total amount of the diamines, the tensile
modulus may substantially be deteriorated.
[0123] The dicarbonyl compound represented by Chemical Formula 2
and the tetracarboxylic acid dianhydride represented by Chemical
Formula 3 may be included in a mole ratio of 10 to 80:90 to 20, for
example, 10 to 70:90 to 30, for example, 10 to 60:90 to 40, for
example, 10 to 50:90 to 50, for example, 10 to 40:90 to 60, and for
example, 10 to 30:90 to 70.
[0124] By including the dicarbonyl compound represented by Chemical
Formula 2 and tetracarboxylic acid dianhydride represented by
Chemical Formula 3 at a mole ratio of the above, the prepared
poly(amide-imide) copolymer may have improved mechanical
properties, such as, for example, an improved toughness, while
maintaining excellent optical properties, such as, for example, a
high transmittance, a low Yellowness Index (YI), a small color
change after exposing to Ultra Violet (UV) light, a low haze, and
the like. For example, the poly(amide-imide) copolymer according to
an embodiment may have a transmittance of about greater than or
equal to about 89% at a wavelength range of 350 nanometers to 750
nanometers, YI of less than 2.0, less than 1.1 of YI increase after
exposure to an ultraviolet (UV) lamp of a UVB wavelength region for
72 hours, and a toughness of greater than or equal to 1,000
Joulm.sup.-310.sup.4. Further, the poly(amide-imide) copolymer may
have a low T.sub.g of less than 270.degree. C.
[0125] The tetracarboxylic acid dianhydride represented by Chemical
Formula 3 may be a combination of the compound represented by
Chemical Formula 3 wherein R.sup.10 is a single bond, and both n7
and n8 are 0, and the compound represented by Chemical Formula 3
wherein R.sup.10 is --C(C.sub.nF.sub.2n+1).sub.2-- wherein
1.ltoreq.n.ltoreq.10, and both n7 and n8 are 0, in a mole ratio of
1:5 to 10, for example, 1:5 to 9, and for example, 1:6 to 8. In an
exemplary embodiment, the tetracarboxylic acid dianhydride
represented by Chemical Formula 3 may be a combination of
3,3',4,4'-biphenyl tetracarboxylic dianhydride (BPDA) and
4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), and in
this case, by including BPDA and 6FDA in the above ratio, the
prepared poly(amide-imide) copolymer may have good optical
properties, as well as improved mechanical properties.
[0126] When R.sup.10 is a single bond in the tetracarboxylic acid
dianhydride represented by Chemical Formula 3, the tetracarboxylic
acid dianhydride has much more rigid structure than those having
different groups as said R.sup.10. It has been known that as the
amount of the tetracarboxylic acid dianhydride having rigid
structure increases, mechanical properties of the prepared
poly(amide-imide) copolymer increases. However, although the
poly(amide-imide) copolymer according to an embodiment is prepared
from a reactant wherein the amount of the tetracarboxylic acid
dianhydride represented by Chemical Formula 3 having R.sup.10 which
is not a single bond is greater than that having R.sup.10 which is
a single bond, the poly(amide-imide) copolymer has improved
mechanical properties, such as, for example, a high toughness of
greater than or equal to about 1,000 Joulm.sup.-310.sup.4, while
maintaining good optical properties, such as, for example, a high
light transmittance, for example, greater than or equal to about
89% in a wavelength range of 350 nm to 750 nm, and a YI of less
than or equal to 2.0. Without being bound to a specific theory, it
is understood that these results may derive from the improved
flexibility of the poly(amide-imide) copolymer according to an
embodiment prepared by polymerizing a composition including a
substituted or unsubstituted linear aliphatic diamine.
[0127] Accordingly, the poly(amide-imide) copolymer according to an
embodiment having excellent optical and mechanical properties may
be advantageous for a use in a display device, such as, for
example, as a window film for a flexible display device.
[0128] Another embodiment provides a composition for preparing a
poly(amide-imide) copolymer including a substituted or
unsubstituted linear aliphatic diamine, a compound represented by
Chemical Formula 4, and a tetracarboxylic acid dianhydride
represented by Chemical Formula 3:
##STR00018##
[0129] wherein, in Chemical Formula 4,
[0130] R.sup.3 is a substituted or unsubstituted phenylene or a
substituted or unsubstituted biphenylene group,
[0131] n0 is a number greater than or equal to 0,
[0132] Ar.sup.1 and Ar.sup.2 are each independently represented by
Chemical Formula 5:
##STR00019##
[0133] wherein, in Chemical Formula 5,
[0134] R.sup.6 and R.sup.7 are each independently an electron
withdrawing group selected from --CF.sub.3, --CCl.sub.3,
--CBr.sub.3, --Cl.sub.3, --NO.sub.2, --CN, --C(.dbd.O)CH.sub.3, and
--CO.sub.2C.sub.2H.sub.5,
[0135] R.sup.8 and R.sup.9 are each independently a halogen, a
hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic
organic group, a substituted or unsubstituted C6 to C20 aromatic
organic group, an alkoxy group of formula --OR.sup.204, wherein
R.sup.204 is a C1 to C10 aliphatic organic group, or a silyl group
of formula --SiR.sup.205R.sup.206R.sup.207 wherein R.sup.205,
R.sup.206, and R.sup.207 are each independently hydrogen or a C1 to
C10 aliphatic organic group,
[0136] n3 is an integer ranging from 1 to 4, n5 is an integer
ranging from 0 to 3, provided that n3+n5 is an integer ranging from
1 to 4, and
[0137] n4 is an integer ranging from 1 to 4, n6 is an integer
ranging from 0 to 3, provided that n4+n6 is an integer ranging from
1 to 4;
##STR00020##
[0138] wherein, in Chemical Formula 3,
[0139] R.sup.10 is a single bond, --O--, --S--, --C(.dbd.O)--,
--CH(OH)--, --C(.dbd.O)NH--, --S(.dbd.O).sub.2--,
--Si(CH.sub.3).sub.2--, --(CH.sub.2).sub.p--, --(CF.sub.2).sub.q--,
--C(C.sub.nH.sub.2n+1).sub.2--, --C(C.sub.nF.sub.2n+1).sub.2--,
--(CH.sub.2).sub.pC(C.sub.nH.sub.2n+1).sub.2(CH.sub.2).sub.q--, or
--(CH.sub.2).sub.pC(C.sub.nF.sub.2n+1).sub.2(CH.sub.2).sub.q--
wherein 1.ltoreq.n.ltoreq.10, 1.ltoreq.p.ltoreq.10, and
1.ltoreq.q.ltoreq.10,
[0140] R.sup.12 and R.sup.13 are each independently a halogen, a
hydroxy group, a substituted or unsubstituted C1 to C10 aliphatic
organic group, a substituted or unsubstituted C6 to C20 aromatic
organic group, an alkoxy group of formula --OR.sup.201, wherein
R.sup.201 is a C1 to C10 aliphatic organic group, or a silyl group
of formula --SiR.sup.210R.sup.211R.sup.212, wherein R.sup.210,
R.sup.211, and R.sup.212 are each independently hydrogen ora C1 to
C10 aliphatic organic group, and
[0141] n7 and n8 are each independently an integer ranging from 0
to 3.
[0142] R.sup.3 of Chemical Formula 3 may be an unsubstituted
phenylene group, both R.sup.6 and R.sup.7 may be --CF.sub.3, both
n3 and n4 may be 1, and both n5 and n6 may be 0 (zero).
[0143] As described above, in a conventional method for preparing a
poly(amide-imide) copolymer, an amide structural unit may first be
prepared by a reaction of a dicarbonyl compound and a diamine, and
then an additional diamine and a dianhydride compound are added to
the reactor to prepare an amic acid structural unit, as well as a
poly(amide-imide) copolymer by linking the amide structural unit
and the amic acid structural unit. Meanwhile, in the process of
preparing the amide structural unit, there is a problem that a
by-product, such as, halogenated hydrogen (HX: `H` indicates
hydrogen, and `X` indicates halogen), for example, hydrogen
chloride (HCI), is produced. The hydrogen chloride by-product
causes corrosion of an element of an apparatus, and thus, should
necessarily be removed by a precipitation process. In order to
remove the by-product, an HX scavenger, such as a tertiary amine,
may be added to the reactor, whereby a salt of HX is produced
(please see Reaction Scheme 1 below). If the produced salt of HX is
not removed and a film is produced therefrom, serious deterioration
of optical properties of the produced film occurs. Therefore, a
precipitation process to remove the salt of HX is required in the
conventional method for preparing poly(amide-imide) copolymer. The
precipitation process increases total process time and cost, while
reducing the yield of the final poly(amide-imide) copolymer
produced therefrom.
##STR00021##
[0144] In addition to using the conventional method including the
precipitation process as described above, it is also possible to
prepare a poly(amide-imide) copolymer according to an embodiment by
first reacting a diamine and a dicarbonyl compound to prepare an
amide structural unit-containing oligomer having amino groups
located at both ends thereof (hereinafter, referred to as "an amide
structural unit-containing oligomer"), and then reacting the
prepared amide structural unit-containing oligomer as a diamine
monomer with a tetracarboxylic acid dianhydride to provide a
poly(amide-imide) copolymer. According to the new method for
preparing a poly(amide-imide) copolymer, the precipitation process
for removing the HX salt may be omitted, and thus, not only the
total process time and cost may be reduced, but also the yield of
the final poly(amide-imide) copolymer may increase. Further, it is
also possible to obtain a poly(amide-imide) copolymer including a
higher amount of an amide structural unit than those prepared by
using the conventional method, and thus, an article prepared from
the poly(amide-imide) copolymer, for example, a film, may have
further improved mechanical properties, while maintaining good
optical properties.
[0145] Accordingly, another embodiment provides a composition for
preparing a poly(amide-imide) copolymer including an amide
structural unit-containing oligomer represented by Chemical Formula
4 as a diamine monomer, which may be prepared by reacting a diamine
and a dicarbonyl compound, a tetracarboxylic acid dianhydride
represented by Chemical Formula 3 for reacting with the oligomer to
provide an imide structural unit, and as an additional diamine, a
substituted or unsubstituted linear aliphatic diamine for reacting
with the tetracarboxylic acid dianhydride represented by Chemical
Formula 3 to provide an imide structural unit.
[0146] The compound represented by Chemical Formula 4 may be
prepared by reacting a dicarbonyl compound represented by Chemical
Formula 2 in which R.sup.3 is a substituted or unsubstituted
phenylene group or a substituted or unsubstituted biphenylene
group, and one or two diamine(s) represented by Chemical Formula 1
in which A is represented by Chemical Formula 5, wherein the
diamine represented by Chemical Formula 1 may be added in a greater
amount than the dicarbonyl compound represented by Chemical Formula
2 to provide an oligomer having amino groups at both ends thereof.
In this case, there may be a remaining diamine that does not react
with the dicarbonyl compound, which may also be represented by
Chemical Formula 4, wherein n0 is 0 (zero). Accordingly, the
diamine represented by Chemical Formula 4 wherein n0 is 0 may also
be reacted with a tetracarboxylic acid dianhydride represented by
Chemical Formula 3 along with the compound represented by Chemical
Formula 4 wherein n0 is greater than or equal to 1 to prepare an
imide structural unit.
[0147] In an embodiment, the composition may further include a
diamine represented by Chemical Formula 1:
NH.sub.2-A-NH.sub.2 Chemical Formula 1
[0148] wherein in Chemical Formula 1,
[0149] A is a ring system including two or more C6 to C30 aromatic
rings linked by a single bond, wherein each of the two or more
aromatic rings is independently unsubstituted or substituted by an
electron-withdrawing group.
[0150] In an exemplary embodiment, the diamine represented by
Chemical Formula 1 may have a ring system including two C6 to C12
aromatic rings linked by a single bond, wherein each of the two C6
to C12 aromatic rings may independently be substituted by an
electron-withdrawing group selected from an halogen atom, a nitro
group, a cyano group, a C1 or C2 haloalkyl group, a C2 to C6
alkanoyl group, or a C1 to C6 ester group.
[0151] In an exemplary embodiment, the diamine represented by
Chemical Formula 1 may include at least one selected from the
diamines represented by the following chemical formulae:
##STR00022##
[0152] The diamine represented by Chemical Formula 1 may include a
diamine represented by Chemical Formula A, i.e.,
2,2'-bis(trifluoromethyl)benzidine (TFDB):
##STR00023##
[0153] The tetracarboxylic acid dianhydride represented by Chemical
Formula 3 may be a combination of the compound represented by
Chemical Formula 3-1 and the compound represented by Chemical
Formula 3-2, but is not limited thereto:
##STR00024##
[0154] The compound represented by Chemical Formula 3-1 may be
6FDA, the compound represented by Chemical Formula 3-2 may be at
least one of s-BPDA, a-BPDA, and i-BPDA, and in an exemplary
embodiment, the compound represented by Chemical Formula 3-2 may be
s-BPDA.
[0155] In an exemplary embodiment, an amount of the substituted or
unsubstituted linear aliphatic diamine may be less than 90 mole %,
for example, greater than 20 mole % and less than 90 mole %, for
example, greater than or equal to about 25 mole % and less than or
equal to about 85 mole %, and for example, greater than or equal to
about 30 mole % and less than or equal to about 80 mole %, based on
the total mole number of the substituted or unsubstituted linear
aliphatic diamine and any other diamines required to prepare the
poly(amide-imide) copolymer, which also include the diamine needed
to prepare the compound represented by Chemical Formula 4.
[0156] Explanations for the substituted or unsubstituted linear
aliphatic diamine, the diamine represented by Chemical Formula 1,
the dicarbonyl compound represented by Chemical Formula 2, and the
tetracarboxylic acid dianhydride represented by Chemical Formula 3
are the same as those described above for the poly(amide-imide)
copolymer according to an embodiment, and thus, a more detailed
explanation for the compounds are omitted here.
[0157] After preparing a poly(amide-imide) copolymer from the
composition, an article may be formed from the poly(amide-imide)
copolymer through a dry-wet method, a dry method, or a wet method,
but is not limited thereto. When the article is a film, it may be
manufactured using a solution including the composition through the
dry-wet method, wherein a layer is formed by extruding the solution
of the composition from a mouth piece on a supporter, such as drum
or an endless belt, drying the layer by evaporating the solvent
from the layer until the layer has a self-maintenance property. The
drying may be performed by heating, for example, from about
25.degree. C. to about 150.degree. C., within about 1 hour or less.
Then, the dried layer may be heated from the room temperature to
about 250.degree. C. or to about 300.degree. C. at a heating rate
of about 10.degree. C. per minute, and then be allowed to stand at
the heated temperature for about 5 minutes to about 30 minutes to
obtain a polyimide-based film.
[0158] When the surface of the drum and/or the endless belt used
for the drying process becomes flat, a layer with a flat surface is
formed. The layer obtained after the drying process is delaminated
from the supporter, and subjected to a wet process, desalted,
and/or desolventized. The manufacturing of the film is completed
after the layer is elongated, dried, and/or heat treated. The heat
treatment may be performed at about 200.degree. C. to about
500.degree. C., for example, at about 250.degree. C. to about
400.degree. C., for several seconds to several minutes. After the
heat treatment, the layer may be cooled slowly, for example, at a
cooling rate of less than or equal to about 50.degree. C. per
minute.
[0159] The layer may be formed as a single layer or multiple
layers.
[0160] When prepared as a film, the film may have a yellowness
index (YI) of less than or equal to 2.1 at a thickness of about 35
micrometers (.mu.m) to about 100 .mu.m according to an ASTM D1925
method, and a light transmittance of greater than or equal to 89%
in a wavelength range of 350 nm to 750 nm. Further, the yellowness
difference (.DELTA.YI) before and after exposure to UVB lamp
(greater than or equal to 200 millijoules per square centimeter,
mJ/cm.sup.2) for 72 hours may be less than 1.1, for example, less
than or equal to 0.95, and a refractive index may be less than or
equal to 1.68, which prove very good optical properties. Further,
toughness of the film may be greater than or equal to 1,000
Joulm.sup.-310.sup.4, which proves good mechanical properties.
[0161] That is, the article may maintain excellent optical
properties of a poly(amide-imide) copolymer, such as, for example,
a low YI and high light transmittance, while having an improved and
high toughness, and thus, may be advantageous for a use as a window
film for a flexible display device.
[0162] Hereafter, the technology of this disclosure is described in
detail with reference to examples. The following examples and
comparative examples are not restrictive but are illustrative
only.
EXAMPLES
Synthesis Example 1
Preparation of an Oligomer Containing 70 mole % of an Amide
Structural Unit as a Diamine Monomer
[0163] An amide structural unit-containing oligomer, as a diamine
monomer, is prepared by reacting TPCI and
2,2'-bis(trifluoromethyl)benzidine (TFDB), in accordance with
Reaction Scheme 2:
##STR00025##
[0164] That is, 1 mole equivalent (0.122 mole, 39.2 grams) of
2,2'-bis(trifluoromethyl)benzidine (TFDB) and 2.8 mole equivalent
(0.343 mole, 27.11 grams) of pyridine are dissolved in 700 g of
N,N-dimethyl acetamide (DMAc) as a solvent in a round-bottomed
flask, and 50 milliliters (mL) of DMAc is further added to the
flask to dissolve the remaining TFDB. Then, 0.7 mole equivalent
(0.086 mole, 17.4 g) of terephthaloyl chloride (TPCI) is divided
into 4 portions, which are individually added, each portion at a
time, to be mixed with the TFDB solution. The mixture is then
vigorously stirred and reacted for 15 minutes at room
temperature.
[0165] The resultant solution is further stirred under a nitrogen
atmosphere for 2 hours, and then added to 7 liters of water
containing 350 g of NaCl. The resulting mixture is stirred for 10
minutes. Subsequently, a solid produced therein is filtered,
re-suspended twice by using 5 liters (L) of deionized water, and
then re-filtered. The water remaining in the final product on the
filter is removed to the extent possible by thoroughly pressing the
filtered precipitate on a filter. The precipitate is then dried at
90.degree. C. under vacuum for 48 hours, to obtain an amide
structural unit-containing oligomer represented in Reaction Scheme
2, as a diamine monomer, as a final product. The prepared oligomer
containing 70 mol % of amide structural unit has a number average
molecular weight of about 997 grams per mole (gram/mole).
EXAMPLES AND COMPARATIVE EXAMPLE
Preparation of poly(amide-imide) Copolymer Films
Example 1
[0166] 168 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 17.327
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, 8.171 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB), and 3.271 g of
hexamethylene diamine (NMDA) are added thereto and dissolved, and
the temperature is set to 25.degree. C. Then, 3.231 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 24.336
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
5.20 grams of pyridine and 20.14 grams of acetic anhydride are
added thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 11.2 weight %.
[0167] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a convention oven, wherein the
temperature is increased from the room temperature to 200.degree.
C., at a heating rate of 3.degree. C. per minutes, maintained at
200.degree. C. for about 20 minutes, and slowly cooled to room
temperature to obtain a poly(amide-imide) copolymer film.
Example 2
[0168] 136 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 7.642
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, 2.276 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB), and 1.925 g of
hexamethylene diamine (NMDA) are added thereto and dissolved, and
the temperature is set to 25.degree. C. Then, 1.425 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 10.733
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
2.29 grams of pyridine and 8.88 grams of acetic anhydride are added
thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 14 weight %.
[0169] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a convention oven, wherein the
temperature is increased from the room temperature to 200.degree.
C., at a heating rate of 3.degree. C. per minutes, maintained at
200.degree. C. for about 20 minutes, and slowly cooled to room
temperature to obtain a poly(amide-imide) copolymer film.
Example 3
[0170] 136 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 7.921
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, 0.982 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB), and 2.495 g of
hexamethylene diamine (NMDA) are added thereto and dissolved, and
the temperature is set to 25.degree. C. Then, 1.477 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 11.125
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
2.38 grams of pyridine and 9.21 grams of acetic anhydride are added
thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 14 weight %.
[0171] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a convention oven, wherein the
temperature is increased from the room temperature to 200.degree.
C., at a heating rate of 3.degree. C. per minutes, maintained at
200.degree. C. for about 20 minutes, and slowly cooled to room
temperature to obtain a poly(amide-imide) copolymer film.
Example 4
[0172] 152 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 20.203
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, and 6.293 g of hexamethylene
diamine (HMDA) are added thereto and dissolved, and the temperature
is set to 25.degree. C. Then, 17.176 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 14.3
grams of 4,4'- (hexafluoroisopropylidene)diphthalic anhydride
(6FDA) are added thereto, and the mixture is stirred for 48 hours.
Then, 5.39 grams of pyridine and 20.86 grams of acetic anhydride
are added thereto, and the mixture is stirred for 24 hours to
obtain a poly(amic acid-amide) copolymer solution, of which the
solid content is 11.2 weight %.
[0173] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a convention oven, wherein the
temperature is increased from the room temperature to 200.degree.
C., at a heating rate of 3.degree. C. per minutes, maintained at
200.degree. C. for about 20 minutes, and slowly cooled to room
temperature to obtain a poly(amide-imide) copolymer film.
Example 5
[0174] 120 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 7.930
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, 4.735 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB), and 4.007 g of
hexamethylene diamine (HMDA) are added thereto and dissolved, and
the temperature is set to 25.degree. C. Then, 2.321 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 21.006
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
4.36 grams of pyridine and 16.90 grams of acetic anhydride are
added thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 22.1 weight %.
[0175] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a convention oven, wherein the
temperature is increased from the room temperature to 200.degree.
C., at a heating rate of 3.degree. C. per minutes, maintained at
200.degree. C. for about 20 minutes, and slowly cooled to room
temperature to obtain a poly(amide-imide) copolymer film.
Example 6
[0176] 120 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 10.681
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, 0.427 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB), and 5.383 g of
hexamethylene diamine (NMDA) are added thereto and dissolved, and
the temperature is set to 25.degree. C. Then, 2.340 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 21.17
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
4.40 grams of pyridine and 17.03 grams of acetic anhydride are
added thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 22 weight %.
[0177] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a convention oven, wherein the
temperature is increased from the room temperature to 200.degree.
C., at a heating rate of 3.degree. C. per minutes, maintained at
200.degree. C. for about 20 minutes, and slowly cooled to room
temperature to obtain a poly(amide-imide) copolymer film.
Example 7
[0178] 154 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 10.550
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, and 7.784 g of hexamethylene
diamine (NMDA) are added thereto and dissolved, and the temperature
is set to 25.degree. C. Then, 2.737 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 28.929
grams of 4,4'- (hexafluoroisopropylidene)diphthalic anhydride
(6FDA) are added thereto, and the mixture is stirred for 48 hours.
Then, 2.35 grams of pyridine and 18.24 grams of acetic anhydride
are added thereto, and the mixture is stirred for 24 hours to
obtain a poly(amic acid-amide) copolymer solution, of which the
solid content is 20.4 weight %.
[0179] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a convention oven, wherein the
temperature is increased from the room temperature to 200.degree.
C., at a heating rate of 3.degree. C. per minutes, maintained at
200.degree. C. for about 20 minutes, and slowly cooled to room
temperature to obtain a poly(amide-imide) copolymer film.
Example 8
[0180] 120 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 5.982
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, 1.882 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB), and 5.987 g of
hexamethylene diamine (NMDA) are added thereto and dissolved, and
the temperature is set to 25.degree. C. Then, 2.602 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 23.547
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
4.86 grams of pyridine and 18.94 grams of acetic anhydride are
added thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 21.8 weight %.
[0181] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a convention oven, wherein the
temperature is increased from the room temperature to 200.degree.
C., at a heating rate of 3.degree. C. per minutes, maintained at
200.degree. C. for about 20 minutes, and slowly cooled to room
temperature to obtain a poly(amide-imide) copolymer film.
Comparative Example 1
[0182] 152 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 13.446
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, and 13.199 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB) are added thereto and
dissolved, and the temperature is set to 25.degree. C. Then, 2.125
grams of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and
19.230 grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride
(6FDA) are added thereto, and the mixture is stirred for 48 hours.
Then, 4.0 grams of pyridine and 15.47 grams of acetic anhydride are
added thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 14 weight %.
[0183] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a furnace, wherein the temperature is
increased from the room temperature to 200.degree. C., at a heating
rate of 3.degree. C. per minutes, maintained at 200.degree. C. for
about 20 minutes, and slowly cooled to room temperature to obtain a
poly(amide-imide) copolymer film.
Example 9
[0184] 168 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 15.477
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, 12.660 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB), and 0.976 g of
hexamethylene diamine (NMDA) are added thereto and dissolved, and
the temperature is set to 25.degree. C. Then, 2.886 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 21.738
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
4.65 grams of pyridine and 17.99 grams of acetic anhydride are
added thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 11.3 weight %.
[0185] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a furnace, wherein the temperature is
increased from the room temperature to 200.degree. C., at a heating
rate of 3.degree. C. per minutes, maintained at 200.degree. C. for
about 20 minutes, and slowly cooled to room temperature to obtain a
poly(amide-imide) copolymer film.
Example 10
[0186] 168 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 16.347
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, 10.550 g of
2,2'-bis(trifluoromethyl)benzidine (TFDB), and 2.055 g of
hexamethylene diamine (NMDA) are added thereto and dissolved, and
the temperature is set to 25.degree. C. Then, 3.048 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 22.959
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
4.91 grams of pyridine and 19.0 grams of acetic anhydride are added
thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 11.3 weight %.
[0187] After cooling the poly(amic acid-amide) solution to a
temperature of 25.degree. C., the solution is casted on a glass
substrate, and dried for 40 minutes on a hot plate at a temperature
of 100.degree. C. Then, the film is separated from the glass
substrate and introduced into a furnace, wherein the temperature is
increased from the room temperature to 200.degree. C., at a heating
rate of 3.degree. C. per minutes, maintained at 200.degree. C. for
about 20 minutes, and slowly cooled to room temperature to obtain a
poly(amide-imide) copolymer film.
Example 11
[0188] 150 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 11.514
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, and 8.495 g of hexamethylene
diamine (HMDA) are added thereto and dissolved, and the temperature
is set to 25.degree. C. Then, 11.949 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 18.042
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hour. Then,
2.57 grams of pyridine and 19.90 grams of acetic anhydride are
added thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 22.5 weight %.
[0189] The obtained poly(amide-imide) copolymer solution becomes
gelated as time goes on, and it is not possible to fabricate a film
using the solution as whitening occurs.
Example 12
[0190] 146 grams of N,N-dimethyl acetamide (DMAc) as a solvent is
charged into a 4-neck double-walled 250 mL reactor equipped with a
mechanical stirrer and a nitrogen inlet, while passing nitrogen gas
through, and the temperature is set to 25.degree. C. Then, 13.517
grams of the 70 mol % of amide structural unit-containing oligomer
prepared in Synthesis Example 1, and 9.248 g of hexamethylene
diamine (HMDA) are added thereto and dissolved, and the temperature
is set to 25.degree. C. Then, 16.388 grams of
3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 14.846
grams of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)
are added thereto, and the mixture is stirred for 48 hours. Then,
2.82 grams of pyridine and 21.84 grams of acetic anhydride are
added thereto, and the mixture is stirred for 24 hours to obtain a
poly(amic acid-amide) copolymer solution, of which the solid
content is 24 weight %.
[0191] The obtained poly(amide-imide) copolymer solution becomes
gelated as time goes on, and it is not possible to fabricate a film
using the solution as whitening occurs.
[0192] Evaluation: Evaluation of the Films
[0193] Each of the poly(amide-imide) copolymer films prepared in
Examples 1 to 10 and Comparative Example 1 are evaluated for the
composition, thickness, glass transition temperature, amount of
remaining solvent, optical properties, and mechanical properties,
and the obtained values are described in Table 1 below.
[0194] As for the optical properties, light transmittance in a
wavelength range between 350 nanometers (nm) to 750 nm, YI, YI
difference after exposure UV ray, and haze are measured.
[0195] As for the mechanical properties, toughness and tensile
modulus are measured.
[0196] Thickness of film is determined by using Micrometer
(Mitutoyo Com. Ltd.).
[0197] Glass transition temperature (T.sub.g) is measured according
to ASTM D3418 method by using DMA (Dynamic Mechanical Analyzer)
Q800 apparatus.
[0198] An amount of solvent remained in a film is determined by
using TGA (Thermogravimetric Analyzer) Q500, and by taking the
decrease in weight in the region between 150.degree. C. and
370.degree. C. as the amount of solvent remained in a film.
[0199] Yellowness index (YI), light transmittance (at a wavelength
range of 350 nm to 750 nm), and haze are measured for a film having
a thickness of about 50 micrometers, according to an ASTM D1925
method by using a spectrophotometer, CM-3600d made by Konica
Minolta Inc. YI difference (.DELTA.YI) after and before exposure to
UV light is measured as the YI difference after and before exposure
to an ultraviolet (UV) lamp of a UVB wavelength region for 72
hours.
[0200] Tensile modulus is measured for a sample of a film having a
width of 10 millimeters (mm) and a length of 50 mm by elongating
each sample at a rate of 0.5 mm/minute at the room temperature five
times, according to ASTM D882 method by using Instron 3365
apparatus.
[0201] Toughness is measured according to an ASTM D882 method, and
is determined by calculating the total area by multiplying the X
axis for strain and the Y axis for stress.
TABLE-US-00001 TABLE 1 Solvent Tensile Toughness thickness Tg
remained Tr Haze modulus [Joule Composition [.mu.m] [.degree. C.]
[%] [%] (%) YI .DELTA.YI [GPa] m.sup.-3 10.sup.4] Comparative
TPCI/6FDA/BPDA/TFDB = 52 353.5 3 89.8 0.2 1.66 0.76 4.3 550.7
Example 1 30/60/10/100 Example 9 TPCI/6FDA/BPDA/TFDB/ 48 323.3 2.8
89.8 0.2 1.59 0.66 4.7 669.4 HMDA = 30/60/10/90/10 Example 10
TPCI/6FDA/BPDA/TFDB/ 46 292.9 2.4 89.8 0.1 1.54 0.50 4.6 870.2 HMDA
= 30/60/10/80/20 Example 1 TPCI/6FDA/BPDA/TFDB/ 50 267.9 1.8 89.6
0.3 1.56 0.57 4.7 1498.2 HMDA = 30/60/10/70/30 Example 2
TPCI/6FDA/BPDA/TFDB/ 49 250.5 1.6 89.7 0.7 1.50 0.43 4.5 1658.3
HMDA = 30/60/10/60/40 Example 3 TPCI/6FDA/BPDA/TFDB/ 44 227.3 1.3
89.9 0.4 1.39 0.45 4.2 1862.6 HMDA = 30/60/10/50/50 Example 4
TPCI/6FDA/BPDA/TFDB/ 52 223.2 1.3 89.9 0.3 1.59 0.65 4.1 1876.3
HMDA = 30/60/10/43/57 Example 5 TPCI/6FDA/BPDA/TFDB/ 55 231.7 1.2
89.8 0.5 1.56 0.72 4.1 1858.4 HMDA = 20/70/10/50/50 Example 6
TPCI/6FDA/BPDA/TFDB/ 55 206.1 0.9 89.9 0.4 1.58 0.54 3.8 1923.6
HMDA = 20/70/10/30/70 Example 7 TPCI/6FDA/BPDA/TFDB/ 55 189.1 0.7
90.3 0.3 1.55 1.03 3.5 1950.4 HMDA = 20/70/10/28/72 Example 8
TPCI/6FDA/BPDA/TFDB/ 55 178.1 0.6 89.8 0.5 1.53 0.92 3.4 2200.4
HMDA = 10/80/10/20/80
[0202] As shown in Table 1, the films prepared by including the
linear aliphatic diamine, HMDA (hexamethylene diamine) in an amount
from 30 mol % to 80 mol % according to Examples 1 to 8 have
increased tensile moduli, and moreover, increased toughness by more
than 2 times, compared with the film according to Comparative
Example 1, which is prepared by not including the linear aliphatic
diamine. Meanwhile, when compared with the films according to
Examples 9 and 10, which are prepared by including less than or
equal to 20 mol % of HMDA, the films according to Examples 1 to 8
show hardly changed tensile moduli or a slightly decreased tensile
moduli, while greatly increased toughness.
[0203] Further, while the film according to Comparative Example 1,
which does not included HMDA, has a T.sub.g of greater than
350.degree. C., the film according to Example 1, which includes
HMDA in an amount of 30 mol %, has a T.sub.g of 267.9.degree. C.,
the T.sub.g decreases as much as about 100.degree. C. As the amount
of HMDA increases as in Examples 2 to 10, toughness increases and
T.sub.g decreases. As T.sub.g of the films according to Examples 1
to 10 decreases, the amount of solvent remained in the films
decreases. While the amount of solvent of the film according to
Comparative Example 1, which does not include HMDA, is 3%, the film
according to Example 1 that includes HMDA in an amount of 30 mol %
has 1.8% of the solvent remained in the film. That is, as the
amount of HMDA increases, the amount of solvent remained decreases
by less than a half.
[0204] Meanwhile, as described above, the films according to
Examples 1 to 10 maintain good optical properties, while having
improved mechanical properties, such as, for example, toughness.
The films according to Examples 1 to 10 have transmittance of
greater than or equal to 89%, which is equivalent or in some cases
(Examples 3, 4, 6, and 7) superior to the films according to
Comparative Example 1, which does not include HMDA. Yl is also
maintained as the films according to Examples 1 to 10 have a YI
less than or equivalent to the YI value of the film according to
Comparative Example 1. Yl difference (.DELTA.YI) and haze of the
films according to Examples 1 to 10 are also maintained compared
with that according to Comparative Example 1.
[0205] As a result, the poly(amide-imide) copolymer prepared by
including a linear aliphatic diamine along with an aromatic diamine
has improved mechanical properties, such as, for example, a
toughness, while maintaining good optical properties, as well as
having a lowered T.sub.g to decrease a process temperature for
fabricating a film. Further, the poly(amide-imide) copolymer film
according to an embodiment that has a lowered T.sub.g has decreased
solvent remained in the film due to the lowered T.sub.g.
[0206] As described above, the poly(amide-imide) copolymer
according to an embodiment prepared by reacting an aromatic
diamine, an aromatic tetracarboxylic dianhydride, and an aromatic
dicarbonyl compound, as well as a linear aliphatic diamine, has
improved mechanical properties, such as, for example, a toughness,
while maintaining good optical properties, and has a lowered
T.sub.g to reduce a process temperature, which leads to the cost
reduction, as well as reduction of the amount of solvent remained
in the final article prepared from the poly(amide-imide) copolymer
to have a more improved quality. Accordingly, the article having
good optical and mechanical properties may be advantageous for use
in a display device, such as, for example, a flexible display
device.
[0207] While this disclosure has been described in connection with
what is presently considered to be practical exemplary embodiments,
it is to be understood that the present disclosure is not limited
to the embodiments presented herein, but on the contrary, is
intended to cover various modifications and equivalent arrangements
included within the spirit and scope of the appended claims.
* * * * *